Process for the manufacture of alkoxylated N-methylol ureas

ABSTRACT

A new process for the manufacture of alkoxylated N-methylol compounds, which comprises reacting 
     A. a N-methylolated organic nitrogen compound with 
     B. an alkylene oxide of the formula ##STR1## wherein R denotes hydrogen, alkyl with 1 to 3 carbon atoms, phenyl or a ##STR2## radical, in the presence of C. AT LEAST ONE METAL ALCOHOLATE OF THE FORMULA 
     
         Me(O--X).sub.r (Q).sub.n.sub.-r 
    
     wherein Me denotes a n-valent transition metal of groups IV, V or VI of the periodic system, X denotes alkyl with 1 to 4 carbon atoms, halogenoalkyl with 2 to 4 carbon atoms, phenyl, benzyl or cycloalkyl with at most 12 ring carbon atoms, Q denotes halogen or alkoxy with 1 to 4 carbon atoms, r denotes 1 to n and n denotes 4, 5 or 6, or in the present of said component (c) together with (d) at least one alkali metal hydroxide or one alkali metal alcoholate of an alkanol with 1 to 4 carbon atoms, at a temperature of 10° to 160° C and a pressure of 1 to 20 atmospheres gauge.

This is a divisional of application Ser. No. 344,669, filed on Mar. 26,1973, now U.S. Pat. No. 4,013,655.

The invention relates to a process for the manufacture of alkoxylatedN-methylol compounds, characterised in that

A. a N-methylolated organic nitrogen compound is reacted with

B. an alkylene oxide of the formula ##STR3## wherein R denotes phenyl,alkyl with 1 to 3 carbon atoms, a ##STR4## radical or, preferably,hydrogen, in the presence of C. AT LEAST ONE METAL ALCOHOLATE OF THEFORMULA

    2. Me(O--X).sub.r (Q).sub.n-r

wherein Me denotes a n-valent transition metal of groups IV, V or VI ofthe periodic system, X denotes phenyl, benzyl, cycloalkyl with at most12, especially 5 to 12, and above all 8 to 12, ring carbon atoms,halogenoalkyl with 2 to 4 carbon atoms, or preferably, alkyl with 1 to 4carbon atoms, Q denotes halogen or alkoxy with 1 to 4 carbon atoms, rdenotes 1 to n and n denotes 4, 5 or 6, and optionally (d) at least onealkali metal hydroxide or one alkali metal alcoholate of an alkanol with1 to 4 carbon atoms, at a temperature of 10° to 160° C. and a pressureof 1 to 20 atmospheres gauge.

The components (a) are as a rule addition products of formaldehyde tonitrogen compounds which can be methylolated such as, for example, ureaor thiourea compounds, 1,3,5-aminotriazines or carboxylic acid amides.

Examples of suitable urea and thiourea compounds are urea, thiourea,substituted ureas such as alkylureas and arylureas, alkyleneureas andalkylenediureas, such as ethyleneurea propyleneurea,dihydroxyethyleneurea, hydroxypropyleneurea and acetylenediurea, andalso dicyandiamide, dicyandiamidine, urones and hexahydropyrimidones.

As examples of 1,3,5-aminotriazines there may be mentioned: melamine andN-substituted melamines, such as N-butylmelamine,N-trihalogenomethylmelamines, triazones, ammeline, guanamines, forexample benzoguanamines and acetoguanamines, or diguanamines.

In general, products which are as highly methylolated as possible yieldparticularly valuable products. Partial ethers of such methylolcompounds with, for example, alkanols with 1 to 22 carbon atoms, such asmethanol, ethanol, n-propanol, isopropanol, n-butanol or octadecylalcohol can also be used.

The N-methylolated carboxylic acid amides are, for example, amides ofaromatic or aliphatic carboxylic acids, such as benzoic acids optionallysubstituted by lower alkyl, lower alkoxy, hydroxyl or halogen, or,preferably, amides of saturated or unsaturated aliphatic carboxylicacids. Particularly suitable compounds of this nature are N-methylolatedaliphatic carboxylic acid amides with at most 22 carbon atoms, above allN-methylolated alkylmonocarboxylic acid amides or alkenylmonocarboxylicacid amides with 3 to 22, preferably 10 to 18, carbon atoms. Asexamples, the mono- or di-N-methylolated amides of, for example, stearicacids, palmitic acid, lauric acid, hydroabietic acid, oleic acid,linoleic acid, linolenic acid, caprylic acid, butyric acid, acrylic acidand methacrylic acid may be mentioned here.

Preferably, N-methylolated 1,3,5-aminotriazines ureas or aliphaticcarboxylic acid amides with at most 22 carbon atoms are used ascomponent (a) in the process according to the invention. Amongst thesecomponents, N-methylolmelamines and N-methylolureas are of greatpractical interest.

Compounds of the formula C., ##STR5## wherein Y denotes alkyl with 1 to4 carbon atoms or, preferably, hydrogen or methylol and Z denotes alkylwith 1 to 22 carbon atoms, alkenyl with 3 to 22 carbon atoms, amonoalkylene glycol or polyalkylene glycol radical with 2 or 3 carbonatoms per alkylene unit and with up to 100 alkoxy groups in the chain,cycloalkyl with 5 to 14, preferably 8 to 12, ring carbon atoms, phenylor benzyl, or N-methylolmelamines with 2 to 6, optionally partiallyetherified methylol groups, for example 1 to 5 methylol groupsetherified with an alkanol having 1 to 22 carbon atoms, especially withmethanol, butanol or octadecylalcohol, have proved particularlysuitable.

The radical Z is derived, for example, from n-butanol, lauryl alcohol,stearyl alcohol, oleyl alcohol, behenyl alcohol, ricinol, cetyl alcohol,cyclohexanol, cyclododecanol, p-nonylcyclohexanol, hydroabietyl alcohol,benzyl alcohol or phenol.

Amongst the compounds of the formula (3), those of the formula ##STR6##wherein Y₁ denotes hydrogen or methylol and Z₁ represents alkyl oralkenyl each with 4 to 18, preferably 10 to 18, carbon atoms, benzyl, amonoethylene glycol or polyethylene glycol radical with 1 to 25 ethoxyradicals in the chain or a monopropylene glycol or polypropylene glycolradical with 1 to 25 propoxy radicals in the chain are above allparticularly suitable.

Typical representatives of components (a) which are suitable for theprocess according to the invention are, for example ##STR7##

The component (b) is, for example, ethylene oxide, propylene oxide,styrene oxide or diglycidyl ether. Propylene oxide and above allethylene oxide are preferred.

The component (c) is as a rule an alcoholate of transition metals ofgroups IV, V or VI of the 4th, 5th or 6th period of the periodic systemaccording to "Lange's Handbook of Chemistry", 10th edition, 1967, pages60 and 61. These transition metals, also called elements of theintermediate groups, of groups a or of groups b, include titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten. The process is appropriately carried out in the presenceof metal alcoholates of the formula

    (8) Me.sub.1 (O--X).sub.n

wherein Me₁ denotes niobium^(V), tantalum^(V), tungsten^(VI),molybdenum^(VI), zirconium^(IV) or hafnium^(IV) and n denotes 4, 5 or 6,depending on the valency of the metal, and X has the indicated meaning.

Preferred metal alcoholates correspond to the formula

    (9) Me.sub.2 (O--X).sub.n.sbsb.1 '

wherein Me₂ denotes zirconium^(IV), niobium^(V), tantalum^(V)tungsten^(VI) and n₁ denotes 4, 5 or 6 and X has the indicated meaning,especially alkyl with 1 to 4 carbon atoms. Amongst these metalalcoholates, niobium alcoholates and tantalum alcoholates with 1 to 4carbon atoms, for example tantalum ethylate and tantalum tert. butylateand niobium ethylate and niobium tert. butylate are particularlyeffective. The radical --O--X in the formulae (2), (8) and (9) ispreferably a radical of an optionally chlorinated alkanol with up to 4carbon atoms, such as, for example, methanol, ethanol, β-chloroethanol,isopropanol, n-propanol, n-butanol, sec.- or tert.-butanol, of acycloalkanol with, appropriately, 5 to 12, or preferably 8 to 12, ringcarbon atoms, such as cyclododecanol, or a radical of phenol or benzylalcohol. As halogen, Q denotes, for example, bromine or preferablychlorine. As alkoxy, Q is as a rule different from OX and can, forexample, be methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy or,preferably, tert. butoxy. r preferably has the same meaning as n, sothat metal alcoholates of the formula Me(OX)_(n) are preferred. Theprocess according to the invention is preferably carried out in thepresence of the optional additional component (d). Such components are,for example, alkali metal hydroxides, such as lithium hydroxide, sodiumhydroxide, potassium hydroxide, rubidium hydroxide or caesium hydroxideor the corresponding alcoholates of alkanols with 1 to 4 carbon atoms,as indicated for the component (c).

Preferably, sodium hydroxide or potassium hydroxide or a sodiumalcoholate or potassium alcoholate of an alkanol with 1 to 4 carbonatoms is used as the component (d).

Relative to the weight of the reaction mixture, 0.05 to 5%, preferably0.1 to 2%, and especially 0.4 to 1%, of the catalysts(c) or (c) and (d)together are advantageously employed.

If the catalysts (c) and (d) are used together, the weight ratio of (c)to (d) is as a rule 9:1 to 1:9, preferably 4:1 to 1:4 or, above all, 7:3to 3:7.

Typical representatives of the component (c) are, for example:

(10.1) Ta(OCH₃)₅

(10.2) ta(OC₂ H₅)₅

(10.3) ta(O--CH(CH₃)₂)₅

(10.4) ta(OC(CH₃)₃)₅ ##STR8## (10.6) Nb(OCH₃)₅ ( 10.7) Nb(OC₂ H₅)₅

(10.8) nb(O--CH(CH₃)₂)₅

(10.9) nb(OC(CH₃)₃)₅ ##STR9## (10.11) W(OCH₃)₆ ( 10.12) W(OC(CH₃)₃)₆

(10.13) hf(O--CH(CH₃)₂)₄

(10.14) hf(O--C(CH₃)₃)₄

(10.15) mo(O--CH(CH₃)₂)₆

(10.16) mo(O--C(CH₃)₃)₆

(10.17) ti(OC₂ H₅)₄

(10.18) ti(O--C(CH₃)₃)₄

(10.19) zr(OC₂ H₅)₄

(10.20) zr(O--C(CH₃)₃)₄

(10.21) ta(OCH₃)Cl₄

(10.22) Nb(OCH₃)₄ Cl

(10.23) Ti(OC₄ H₉)₄

(10.24) zrOCH₃ (OC(CH₃)₃)₄

(10.25) zr(OCH₃)Cl₃

Typical representatives of the component (d) are, for example:

(11.1) LiOH

(11.2) naOH

(11.3) koh

(11.4) liOCH₃

(11.5) naOCH₃

(11.6) naOC₂ H₅

(11.7) naOC(CH₃)₃

(11.8) koch₃

(11.9) koc₂ h₅

(11.10) koc(ch₃)₃

the reaction temperature is preferably 30° to 120° C. or especially 40°to 90° C.

The reaction can be carried out at atmospheric pressure or at an excesspressure of up to 20 atmospheres gauge. Preferably, the pressure is 1 to15 atmospheres gauge or especially 1 to 11 atmospheres gauge. As a rule,the reaction is carried out at the so-called autogenic pressure, that isto say the pressure generated by the reaction mixture itself, at theparticular temperature.

Depending on the end use of the reaction products, 1 to 100, preferably1 to 25, mols of the component (b) are as a rule added onto thecomponent (a).

At times it can be appropriate to carry out the alkoxylation in thepresence of a second alkoxide which does not participate in the actualreaction. For example it is possible to carry out the reaction withethylene oxide and to use propylene oxide or dioxane as the reactionmedium or as the suspension agent.

The process according to the invention has the advantage that alkyleneoxides can be directly added onto a N-methylolated nitrogen compoundunder mild conditions, that is to say at relatively low temperatures andwith a practically neutral catalyst system. It is known that N-methylolcompounds are unstable in even a weakly acid medium and in a stronglyalkaline medium form polycondensates or split off formaldehyde andwater.

Addition reactions of, for example, ethylene oxide to an organiccompound which possesses a mobile hydrogen atom are usually carried outat temperatures of 160° to 200° C. However, at such high temperaturesmost N-methylol compounds are no longer stable, that is to say adegradation of the methylol groups takes place. By means of the catalystsystem used according to the invention (component (c) alone or (c) and(d) together) it has now become possible to carry out such additionreactions successfully even at relatively low temperatures, that is tosay at temperatures below 160° C., without a degradation of the methylolgroups taking place.

Because of their methylol groups or etherified methylol groups theproducts manufactured according to the process of the invention arereactive and can be used for various purposes, depending on thesubstitution. In particular, they are suitable for use as so-calledreactive surface-active agents, that is to say as reactivesurface-active products which under certain conditions, for example inan acid medium or at an elevated temperature, can be converted into anirreversibly insoluble state. They can be used, for example, for themanufacture of micro-capsules. Furthermore, such products are suitablefor use as detergents, detergent additives, emulsifiers, dispersingagents, additives to agents which confirm hydrophobic properties, or assuch agents themselves, agents for imparting a soft handle andhydrophilic properties, or carriers.

Asymmetrical diether compounds which possess at least one hydrophobicand hydrophilic radical, are in particular valuable reactivesurface-active agents.

The introduction of the hydrophilic and hydrophobic groups can becarried out in optional sequence.

In the case of the asymmetrical ethers of dimethylolurea the procedurefollowed is, for example, first to etherify the monomethylolureahydrophobically or hydrophilically. A second molecule of formaldehyde isthen added onto the resulting monoethers of monomethylolurea, to formthe monoether of dimethylolurea. This monoether is again etherifiedhydrophilically or hydrophobically so that an end product which containsboth a hydrophilic and a hydrophobic ether group results.

The introduction of the hydrophilic groups which confer solubility inwater is effected, for example, by reacting the monomethylol compound inquestion, in the presence of a catalyst, with, for example, ethyleneoxide, whereby a polyethylene glycol ether is formed. The hydrophobicgroup is most simply introduced by direct etherification of the methylolgroup in a weakly acid medium with a hydroxyl compound contain 4 or morecarbon atoms. It is optionally also possible first to carry out anetherification with a lower alcohol and to introduce the higher alcoholof low volatility by trans-etherification. A further possibility ofintroducing hydrophobic groups consists of the reaction of the freemethylol groups with, for example, propylene oxide. Since a reactionwith ethylene oxide is carried out in the preceding or subsequent stage,one obtains, for example, dimethylolurea which is etherified on one sidewith propylene oxide and on the other with a polyethylene glycol.

A preferred procedure is, for example, the following: The monomethylolcompound of the urea, which is manufactured in a known manner byaddition of one molecule of formaldehyde, is appropriately firstetherified with n-butanol, and the ethers of the higher alcohols aremanufactured by trans-etherification of the n-butyl-ether. n-Butanol ispreferred because with it the reaction can be carried out in ahomogeneous phase and during the trans-etherification the n-butanol canagain be distilled off in vacuo at a temperature which is notexcessively high. The latter point is important because in theetherification which takes place in a weakly acid medium, for example amedium containing acetic acid, some insoluble carbamide resin is alwaysproduced. When etherifying monomethylolurea with n-butanol it isadvisable to etherify methylolureas containing at least 5% of water,that is to say not to dry them too thoroughly before the etherification.The addition of the ethylene oxide onto the methylol groups of the ureasis carried out in accordance with the process of the invention. Thelength of the polyglycol-ether chain plays an important role because itinfluences the solubility of this surface-active agent, especially thesolubility in water.

The examples which follow explain the invention without restricting itthereto. In the examples, percentages are percentages by weightthroughout.

EXAMPLE 1

100 mg of Ta(OC(CH₃)₃)₅, 6.6 g (corresponding to 8 mols) of ethyleneoxide and 5.4 g of the compound of the formula (5.1) (1 mol) are sealedin a glass tube of 70 ml capacity. The mixture is allowed to react for16 hours at a pressure of 10.5 atmospheres gauge, whilst shaking, in aheating bath thermostatically controlled to 90° C., in the course ofwhich 99% of the ethylene oxide undergo addition. This accordinglyyields an end product which predominantly corresponds to the formula

    (101) H.sub.25 C.sub.12 --O--CH.sub.2 --NH--CO--NH--CH.sub.2 --O--(CH.sub.2 CH.sub.2 O--).sub.8 --H

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                            3,320 cm.sup.-1                                                                         strong                                       Sharp shoulder                                                                          "            2,960 cm.sup.-1                                                                         strong-medium                                Sharp     "            2,920 cm.sup.-1                                                                         weak                                         Sharp     "            2,840 cm.sup.-1                                                                         strong                                       Sharp shoulder                                                                          "            1,710 cm.sup.-1                                                                         strong-medium                                Sharp     "            1,630 cm.sup.-1                                                                         medium                                       Sharp     "            1,575 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,555 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,500 cm.sup.-1                                                                         weak                                         Sharp     "            1,460 cm.sup.-1                                                                         weak-medium                                  Sharp shoulder                                                                          "            1,450 cm.sup.-1                                                                         weak-medium                                  Broad shoulder                                                                          "            1,395 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,380 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,360 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,300 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,290 cm.sup.-1                                                                         weak                                         Broad     "            1,250 cm.sup.-1                                                                         weak-medium                                  Broad     "            1,075 cm.sup.-1                                                                         medium-strong                                Broad     "            1,045 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,030 cm.sup.-1                                                                         medium                                       Sharp     "              920 cm.sup.-1                                                                         weak                                         Broad     "              880 cm.sup.-1                                                                         weak                                         Broad     "              840 cm.sup.-1                                                                         weak                                         Sharp     "              800 cm.sup.-1                                                                         weak                                         Sharp     "              710 cm.sup.-1                                                                         weak-medium                                  Sharp shoulder                                                                          "              660 cm.sup.-1                                                                         weak-medium                                  ______________________________________                                    

EXAMPLE 2

100 mg of Ta(OC(CH₃)₃)₅, 11 g (corresponding to 5 mols) of ethyleneoxide and 14.4 g (1 mol) of the compound of the formula (5.2)(urea-monomethylol-dodecyl-ether post-methylolated withparaformaldehyde) are sealed in a glass tube, as described in Example 1.This reaction mixture is left to react for 16 hours at a pressure of17.5 atmospheres gauge, whilst shaking, in a heating baththermostatically controlled to 110° C., in the course of which 98.7% ofthe ethylene oxide undergo addition. Hence, a reaction product whichpredominantly corresponds to the formula ##STR10## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                            3,400 cm.sup.-1                                                                         medium                                       Sharp shoulder                                                                          "            2,940 cm.sup.-1                                                                         medium-strong                                Sharp     "            2,910 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            2,860 cm.sup.-1                                                                         weak                                         Sharp     "            2,850 cm.sup.-1                                                                         strong                                       Broad shoulder                                                                          "            2,730 cm.sup.-1                                                                         weak                                         Broad     "            1,740 cm.sup.-1                                                                         weak-medium                                  Broad     "            1,710 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,660 cm.sup.-1                                                                         weak-medium                                  Sharp     "            1,650 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,630 cm.sup.-1                                                                         medium                                       Sharp shoulder                                                                          "            1,555 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,535 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,500 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "            1,490 cm.sup.-1                                                                         weak                                         Broad     "            1,455 cm.sup.-1                                                                         weak-medium                                  Broad shoulder                                                                          "            1,370 cm.sup.-1                                                                         weak                                         Sharp     "            1,340 cm.sup.-1                                                                         weak                                         Broad     "            1,285 cm.sup.-1                                                                         weak                                         Broad     "            1,240 cm.sup.-1                                                                         weak                                         Broad     "            1,110 cm.sup.-1                                                                         medium                                       Broad shoulder                                                                          "            1,070 cm.sup.-1                                                                         weak                                         Broad shoulder                                                                          "            1,035 cm.sup. -1                                                                        weak-medium                                  Broad     "              935 cm.sup.-1                                                                         weak                                         Broad     "              880 cm.sup.-1                                                                         weak                                         Broad     "              835 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "              800 cm.sup.-1                                                                         weak                                         Broad     "              750 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "              710 cm.sup.-1                                                                         weak                                         Sharp shoulder                                                                          "              650 cm.sup.-1                                                                         weak                                         ______________________________________                                    

EXAMPLE 3

100 mg of a catalyst mixture of NaOC₂ H₅ and Nb(OC(CH₃)₃)₅ [mixed in theratio of 1:1], 6.6 g of ethylene oxide [corresponding to 6 mols] and6.7g (1 mol) of the compound of the formula (5.3) are sealed in a glasstube, as described in Example 1. This reaction mixture is reacted for 16hours at a pressure of 5.2 atmospheres gauge, whilst shaking, in aheating bath thermostatically controlled to 60° C., in the course ofwhich 98% of the ethylene oxide employed undergo addition.

A reaction product which in the main corresponds to the formula##STR11## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,400 cm.sup.-1                                                                           medium                                      Broad shoulder                                                                          "           2,990 cm.sup.-1                                                                           weak                                        Sharp     "           2,910 cm.sup.-1                                                                           strong                                      Sharp shoulder                                                                          "           2,860 cm.sup.-1                                                                           weak                                        Sharp     "           2,840 cm.sup.-1                                                                           strong                                      Broad shoulder                                                                          "           2,730 cm.sup.-1                                                                           weak                                        Broad     "           1,760 cm.sup.-1                                                                           weak                                        Broad     "           1,705 cm.sup.-1                                                                           weak                                        Broad     "           1,650 cm.sup.-1                                                                           weak-medium                                 Broad shoulder                                                                          "           1,630 cm.sup.-1                                                                           weak-medium                                 Sharp shoulder                                                                          "           1,555 cm.sup.-1                                                                           weak                                        Broad shoulder                                                                          "           1,535 cm.sup.-1                                                                           weak                                        Sharp shoulder                                                                          "           1,500 cm.sup.-1                                                                           weak                                        Sharp     "           1,490 cm.sup.-1                                                                           weak                                        Broad     "           1,455 cm.sup.-1                                                                           weak-medium                                 Sharp shoulder                                                                          "           1,370 cm.sup.-1                                                                           weak                                        Sharp     "           1,340 cm.sup.-1                                                                           weak                                        Broad     "           1,285 cm.sup.-1                                                                           weak                                        Broad     "           1,240 cm.sup.-1                                                                           weak                                        Broad     "           1,110 cm.sup.-1                                                                           strong                                      Broad shoulder                                                                          "           1,065 cm.sup.-1                                                                           weak                                        Broad shoulder                                                                          "           1,030 cm.sup.-1                                                                           weak-medium                                 Broad     "             940 cm.sup. -1                                                                          weak                                        Sharp     "             880 cm.sup.-1                                                                           weak                                        Broad     "             835 cm.sup.-1                                                                           weak                                        Broad shoulder                                                                          "             800 cm.sup.-1                                                                           weak                                        Sharp shoulder                                                                          "             760 cm.sup.-1                                                                           weak                                        Sharp shoulder                                                                          "             745 cm.sup.-1                                                                           weak                                        Broad shoulder                                                                          "             715 cm.sup.-1                                                                           weak                                        Sharp shoulder                                                                          "             655 cm.sup.-1                                                                           weak                                        ______________________________________                                    

EXAMPLE 4

100 mg of a catalyst mixture of KOC₂ H₅ and Nb(OC(CH₃)₃)₅ [in the ratioof 1:1] together with 9.9 g (9 mols) of ethylene oxide and 10.15 g (1mol) of the compound of the formula (5.4) are sealed in a glass tube, asdescribed in Example 1. This mixture is reacted for 16 hours at apressure of 5.2 atmospheres gauge and whilst shaking, in a heating baththermostatically controlled to 60° C., in the course of which 99.4% ofthe ethylene oxide undergo addition. A reaction product whichpredominantly corresponds to the formula

    (104) n--H.sub.37 C.sub.18 --O--CH.sub.2 --NH--CO--NH--CH.sub.2 --O--(CH.sub.2 CH.sub.2 O).sub.9 --H

is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad shoulder                                                                          band at approx.                                                                           3,420 cm.sup.-1                                                                          medium                                       Broad     "           3,350 cm.sup.-1                                                                          medium                                       Sharp shoulder                                                                          "           2,960 cm.sup.-1                                                                          medium-strong                                Sharp     "           2,920 cm.sup.-1                                                                          weak                                         Sharp     "           2,850 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,740 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,730 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,700 cm.sup.-1                                                                          weak                                         Broad     "           1,650 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,625 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,555 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,535 cm.sup.-1                                                                          weak                                         Sharp     "           1,460 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,375 cm.sup.-1                                                                          weak                                         Sharp     "           1,345 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,320 cm.sup.-1                                                                          weak                                         Broad     "           1,290 cm.sup.-1                                                                          weak                                         Broad     "           1,245 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,110 cm.sup.-1                                                                          medium-strong                                Broad shoulder                                                                          "           1,070 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,035 cm.sup.-1                                                                          weak-medium                                  Broad     "             940 cm.sup.-1                                                                          weak                                         Broad     "             885 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             840 cm.sup.-1                                                                          weak                                         Sharp     "             750 cm.sup.-1                                                                          weak                                         Sharp     "             720 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             660 cm.sup.-1                                                                          weak                                         ______________________________________                                    

EXAMPLE 5

100 mg of a catalyst mixture of Ta(OC(CH₃)₃)₅ and NaOC₂ H₅ [in the ratioof 1:1], 8.8 g of ethylene oxide [corresponding to 4 mols] and 5.4 g ofthe compound of the formula (5.5) are sealed in a glass tube. Thismixture is reacted for 16 hours at a pressure of 5.2 atmospheres gaugeand whilst shaking, in a heating bath thermostatically controlled to60°, in the course of which 97% of the ethylene oxide undergo addition.

A reaction product of the formula ##STR12## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad shoulder                                                                          band at approx.                                                                           3,420 cm.sup.-1                                                                          medium                                       Broad     "           3,340 cm.sup.-1                                                                          medium                                       Broad     "           2,920 cm.sup.-1                                                                          medium-strong                                Sharp     "           2,870 cm.sup.-1                                                                          medium-strong                                Broad shoulder                                                                          "           2,740 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,740 cm.sup.-1                                                                          weak                                         Sharp     "           1,705 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,650 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,635 cm.sup.-1                                                                          weak-medium                                  Sharp shoulder                                                                          "           1,560 cm.sup.-1                                                                          weak                                         Sharp     "           1,540 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,510 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,500 cm.sup.-1                                                                          weak                                         Broad     "           1,455 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,440 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,380 cm.sup.-1                                                                          weak                                         Sharp     "           1,350 cm.sup.-1                                                                          weak                                         Broad     "           1,295 cm.sup.-1                                                                          weak                                         Broad     "           1,250 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,220 cm.sup.-1                                                                          weak                                         Broad     "           1,110 cm.sup.-1                                                                          medium-strong                                Broad shoulder                                                                          "           1,070 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,040 cm.sup. -1                                                                         medium                                       Broad     "             940 cm.sup.-1                                                                          weak                                         Sharp     "             885 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             805 cm.sup.-1                                                                          weak                                         Broad     "             745 cm.sup.-1                                                                          weak                                         Sharp     "             700 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             660 cm.sup.-1                                                                          weak                                         ______________________________________                                    

EXAMPLE 6

100 mg of Ta(OC₂ H₅)₅, 13.2 g of ethylene oxide (corresponding to 15mols) and 10 g (1 mol) of the compound of the formula (7.2) are sealedin a glass tube and reacted for 16 hours at a pressure of 10.5atmospheres gauge and whilst shaking, in a heating bath thermostaticallycontrolled to 90° C., in the course of which 100% of the ethylene oxideundergo addition.

A reaction product which predominantly corresponds to the formula##STR13## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,430 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           2,970 cm.sup.-1                                                                          weak-medium                                  Broad     "           2,900 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,850 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,740 cm.sup.-1                                                                          weak                                         Broad     "           2,460 cm.sup.-1                                                                          weak                                         Broad     "           1,710 cm.sup.-1                                                                          weak                                         Sharp     "           1,540 cm.sup.-1                                                                          strong                                       Sharp shoulder                                                                          "           1,470 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,450 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,430 cm.sup.-1                                                                          weak-medium                                  Sharp     "           1,370 cm.sup.-1                                                                          weak-medium                                  Sharp     "           1,340 cm.sup.-1                                                                          weak                                         Sharp     "           1,320 cm.sup.-1                                                                          weak                                         Sharp     "           1,290 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,125 cm.sup.-1                                                                          medium                                       Broad     "           1,085 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,030 cm.sup.-1                                                                          medium                                       Sharp     "             940 cm.sup.-1                                                                          weak                                         Sharp     "             900 cm.sup.-1                                                                          weak                                         Broad     "             850 cm.sup.-1                                                                          weak-medium                                  ______________________________________                                    

EXAMPLE 7

100 mg of a catalyst mixture of NaOH and Nb(OC(CH₃)₃)₅ [in the ratio of1:1] , 3.5 g of ethylene oxide (corresponding to 3 mols) of 7.6 g (1mol) of the compound of the formula (6.1) are sealed in a glass tube.This mixture is reacted for 16 hours at a pressure of 5.2 atmospheresgauge, whilst shaking, in a heating bath thermostatically controlled to60° C., in the course of which 75% of the ethylene oxide undergoaddition. The reaction product in the main corresponds to the formula

    (107) n--H.sub.35 C.sub.17 --CO--NH--CH.sub.2 O--(CH.sub.2 CH.sub.2 O).sub.3 --H

the infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,650 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           3,560 cm.sup.-1                                                                          weak                                         Sharp     "           3,420 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           3,350 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           2,970 cm.sup.-1                                                                          weak-medium                                  Broad     "           2,910 cm.sup.-1                                                                          strong                                       Sharp     "           2,840 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,720 cm.sup.-1                                                                          weak                                         Broad     "           2,460 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,710 cm.sup.-1                                                                          weak                                         Broad     "           1,665 cm.sup.-1                                                                          strong                                       Broad     "           1,585 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,530 cm.sup.-1                                                                          weak                                         Sharp     "           1,490 cm.sup.-1                                                                          weak                                         Sharp     "           1,450 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,410 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,360 cm.sup.-1                                                                          weak                                         Sharp     "           1,340 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,110 cm.sup.-1                                                                          medium-strong                                Broad     "           1,065 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,035 cm.sup.-1                                                                          medium-strong                                Broad     "             925 cm.sup.-1                                                                          weak                                         Sharp     "              875 cm.sup.-1                                                                         weak                                         ______________________________________                                    

EXAMPLE 8

100 mg of Ta(OC(CH₃)₃)₅, 13.2 g of ethylene oxide (corresponding to 6mols) and 9.3 g (1 mol) of the compound of the formula (7.3) are sealedin a glass tube. This reaction mixture is reacted for 16 hours at apressure of 5.2 atmospheres gauge and whilst shaking, in a heating baththermostatically controlled at 60° C., in the course of which 100% ofthe ethylene oxide undergo addition. A reaction product whichpredominantly corresponds to the formula ##STR14## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad shoulder                                                                          band at approx.                                                                           3,400 cm.sup.-1                                                                          strong-medium                                Broad shoulder                                                                          "           3,350 cm.sup.-1                                                                          strong-medium                                Sharp shoulder                                                                          "           2,940 cm.sup.-1                                                                          strong-medium                                Broad shoulder                                                                          "           2,910 cm.sup.-1                                                                          weak                                         Sharp     "           2,860 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,740 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,730 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,630 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,570 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,550 cm.sup.-1                                                                          weak                                         Broad     "           1,500 cm.sup.-1                                                                          weak                                         Broad     "           1,455 cm.sup.-1                                                                          weak-medium                                  Sharp     "           1,345 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,320 cm.sup.-1                                                                          weak                                         Broad     "           1,290 cm.sup.-1                                                                          weak                                         Sharp     "           1,240 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,100 cm.sup.-1                                                                          medium-strong                                Broad shoulder                                                                          "           1,070 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,035 cm.sup.-1                                                                          medium                                       Broad     "             940 cm.sup.-1                                                                          weak-medium                                  Sharp     "             880 cm.sup.-1                                                                          weak                                         Broad     "             840 cm.sup.-1                                                                          weak                                         Sharp     "             810 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "             740 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             655 cm.sup.-1                                                                          weak-medium                                  ______________________________________                                    

EXAMPLE 9

100 mg of Ta(OC₂ H₅)₅, 11 g of ethylene oxide (corresponding to 5 mols)and a mixture of 7.5 g (1 mol) of the compound of the formula (7.4) in7.2 g of propylene oxide (as a suspending agent which can easily beremoved again) are sealed in a glass tube. This mixture is reacted for16 hours at a pressure of 10.5 atmospheres gauge and whilst shaking, ina heating bath thermostatically controlled to 90° C. After removing thepropylene oxide, which has not participated in the reaction, it ispossible to ascertain that 100% of the ethylene oxide have undergoneaddition.

Hence, a reaction product which predominantly corresponds to the formula##STR15## is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,650 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           3,580 cm.sup.-1                                                                          medium                                       Broad     "           3,480 cm.sup.-1                                                                          medium-strong                                Sharp shoulder                                                                          "           2,980 cm.sup.-1                                                                          medium                                       Sharp     "           2,920 cm.sup.-1                                                                          medium                                       Sharp     "           2,860 cm.sup.-1                                                                          medium-strong                                Sharp shoulder                                                                          "           2,800 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           2,780 cm.sup.-1                                                                          weak-medium                                  Broad     "           2,460 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,785 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,745 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,720 cm.sup.-1                                                                          weak                                         Broad     "           1,660 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           1,620 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,580 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,545 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,480 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,450 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,435 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,400 cm.sup.-1                                                                          weak                                         Sharp     "           1,380 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,325 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,140 cm.sup.-1                                                                          weak-medium                                  Sharp     "           1,085 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,040 cm.sup.-1                                                                          medium                                       Sharp     "             965 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             940 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             905 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             880 cm.sup.-1                                                                          weak                                         Sharp     "             860 cm.sup.-1                                                                          weak                                         ______________________________________                                    

EXAMPLE 10

100 mg of a catalyst mixture of KOC₂ H₅ and Nb(OC(CH₃)₃)₅ orTa(OC(CH₃)₃)₅ [in the ratio of 1:1] and 3.5 g of ethylene oxide(corresponding to 4 mols) and 14 g (1 mol) of the compound of theformula (5.6), wherein n=18, are sealed in a glass tube. This mixture isreacted for 16 hours at a pressure of 5.2 atmospheres gauge, whilstshaking, in a heating bath thermostatically controlled to 60° C., in thecourse of which 100% of the ethylene oxide undergo addition. A reactionproduct which predominantly corresponds to the formula

    (110) HO--(C.sub.3 H.sub.6 O).sub.18 --CH.sub.2 --NH--CO--NH--CH.sub.2 O--(CH.sub.2 CH.sub.2 O).sub.4 --H

is obtained.

The starting product of the formula (5.6) can be obtained, for example,if 100 mg of catalyst mixture of KOC₂ H₅ and potassium metal (in theratio of 1:1), a mixture of 26 g of propylene oxide (corresponding to 18mols) and 1.0 g of ethylene oxide (as the starter) and 2.25 g (1 mol) ofmonomethylolurea are sealed in a glass tube. This mixture is reacted for16 hours at a pressure of 5.3 atmospheres gauge and whilst shaking, in aheating bath thermostatically controlled to 90° C., in the course ofwhich 100% of the propylene oxide undergo addition. Instead of the abovecatalyst mixture, a mixture of KOC₂ H₅ and Ta(OC₂ H₅)₅ (in the ratio of1:1) can also be used. This reaction product is thereafter subjected toa post-methylolation with paraformaldehyde. The infra-red spectrum ofthe product (110) shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,360 cm.sup.-1                                                                          strong-medium                                Sharp shoulder                                                                          "           2,950 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           2,910 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           2,860 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           2,720 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,730 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,715 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "           1,650 cm.sup.-1                                                                          weak                                         Sharp     "           1,590 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,450 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "           1,400 cm.sup.-1                                                                          weak                                         Sharp     "           1,370 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,355 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,275 cm.sup.-1                                                                          weak                                         Broad     "           1,235 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,160 cm.sup.-1                                                                          weak-medium                                  Broad     "           1,110 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,075 cm.sup.-1                                                                          weak                                         Broad     "           1,035 cm.sup.-1                                                                          weak                                         Sharp     "             980 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "             930 cm.sup.-1                                                                          weak-medium                                  Sharp     "             880 cm.sup.- 1                                                                         weak                                         Broad     "             830 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             660 cm.sup.-1                                                                          weak-medium                                  ______________________________________                                    

EXAMPLE 11

a. 100 mg of a catalyst mixture of KOC(CH₃)₃ and Ta(OC₂ H₅)₅ [in theratio of 1:1] , 13.2 g (corresponding to 6 mols) of ethylene oxide and4.5 g (1 mol) of monomethylolurea are sealed in a glass tube. Thismixture is reacted for 2 hours at a pressure of 1 - 2 atmospheres gaugeand whilst shaking, in a heating bath which is initially kept at roomtemperature (20° to 25° C.). Thereafter the heating bath isthermostatically controlled to 60° C. and the reaction is continued for16 hours at 5.2 atmospheres gauge, in the course of which 88% of theethylene oxide undergo addition.

b. The reaction product described under (a) is subjected to apost-methylolation with paraformaldehyde and thereafter propylene oxideis added as follows onto this subsequently introduced methylol group.

100 mg of a catalyst mixture of (KOC₂ H₅) and Ta(OC(CH₃)₃)₅ [in theratio of 1:1] , 8.7 g (corresponding to 6 mols) of propylene oxide and9.6 g (1 mol) of the product of the formula (5.7) described under a),wherein n = 6, are sealed in a glass tube. This mixture is reacted,whilst shaking, in a thermostatically controlled heating bath, inaccordance with the following programme: 2 hours at 25° C. and 0.7atmospheres gauge, 4 hours at 60° C. and 2.5 atmospheres gauge and 16hours at 110° C. and 7.9 atmospheres gauge, in the course of which 100%of the propylene oxide undergo addition.

In the main, a reaction product of the formula

    (111) HO--(CH.sub.2 CH.sub.2 O).sub.6 --CH.sub.2 --NH--CO--NH--CH.sub.2 O--(C.sub.3 H.sub.6 O).sub.6 --H

is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad     band at approx.                                                                           3,430 cm.sup.-1                                                                          medium                                       Sharp     "           2,960 cm.sup.-1                                                                          medium-strong                                Sharp shoulder                                                                          "           2,910 cm.sup.-1                                                                          weak                                         Sharp     "           2,860 cm.sup.-1                                                                          strong                                       Broad     "           1,730 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,705 cm.sup.-1                                                                          weak                                         Broad     "           1,645 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,500 cm.sup.-1                                                                          weak                                         Broad     "           1,445 cm.sup.-1                                                                          weak-medium                                  Sharp     "           1,365 cm.sup.-1                                                                          weak                                         Sharp     "           1,340 cm.sup.-1                                                                          weak                                         Sharp     "           1,315 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,280 cm.sup.-1                                                                          weak                                         Broad     "           1,250 cm.sup.-1                                                                          weak                                         Broad     "           1,100 cm.sup.-1                                                                          strong                                       Broad     "           1,030 cm.sup.-1                                                                          weak-medium                                  Broad shoulder                                                                          "             990 cm.sup.-1                                                                          weak                                         Broad     "             945 cm.sup.-1                                                                          weak-medium                                  Broad     "             835 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             740 cm.sup.-1                                                                          weak                                         Sharp shoulder                                                                          "             655 cm.sup.-1                                                                          weak-medium                                  ______________________________________                                    

EXAMPLE 12

100 mg of W(OC(CH₃)₃)₆, 6.6 g (0.15 mol) of ethylene oxide and 8.6 g(0.03 mol) of the compound of the formula (5.1) are sealed in a glasstube. The mixture is allowed to react for 16 hours at a pressure of 4.27atmospheres gauge and whilst shaking, in a heating bath thermostaticallycontrolled to 60° C., in the course of which 99% of the ethylene oxideundergo addition. An end product which predominantly corresponds to theformula

    (112) n--H.sub.25 C.sub.12 --O--CH.sub.2 --NH--CO--NHCH.sub.2 O--(CH.sub.2 CH.sub.2 O).sub.5 --H

is obtained.

The infra-red spectrum of this product shows the following bands:

    ______________________________________                                        Broad shoulder                                                                          band at approx.                                                                           3,400 cm.sup.-1                                                                          strong-medium                                Broad     "           3,330 cm.sup.-1                                                                          medium-strong                                Sharp shoulder                                                                          "           2,950 cm.sup.-1                                                                          strong-medium                                Sharp     "           2,910 cm.sup.-1                                                                          weak                                         Sharp     "           2,850 cm.sup.-1                                                                          strong                                       Broad shoulder                                                                          "           2,740 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,725 cm.sup.-1                                                                          weak                                         Broad     "           1,635 cm.sup.-1                                                                          strong-medium                                Broad     "           1,530 cm.sup.-1                                                                          weak                                         Broad     "           1,490 cm.sup.-1                                                                          weak                                         Broad     "           1,450 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,435 cm.sup.-1                                                                          weak                                         Sharp     "           1,365 cm.sup. -1                                                                         weak                                         Sharp     "           1,340 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,280 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,240 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,170 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,110 cm.sup.-1                                                                          medium                                       Broad shoulder                                                                          "           1,060 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "           1,030 cm.sup.-1                                                                          medium                                       Broad     "             935 cm.sup.-1                                                                          weak                                         Sharp     "             880 cm.sup.-1                                                                          weak                                         Broad     "             835 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             800 cm.sup.-1                                                                          weak                                         Broad     "             765 cm.sup.-1                                                                          weak                                         Broad     "             745 cm.sup.-1                                                                          weak                                         Sharp     "             710 cm.sup.-1                                                                          weak                                         Broad shoulder                                                                          "             660 cm.sup.-1                                                                          weak                                         ______________________________________                                    

EXAMPLE 13

100 mg of Ta(On--C₃ H₇)₅, 7.92 g (corresponding to 6 mols) of ethyleneoxide and 8.64 g (1 mol) of the compound of the formula (5.1) are sealedin a glass tube of 70 ml capacity. The mixture is allowed to react for16 hours at a pressure of 10.5 atmospheres gauge and whilst shaking, ina heating bath thermostatically controlled to 90° C, in the course ofwhich 95.2% of the ethylene oxide undergo addition. A highly viscousclear end product is obtained, which predominantly corresponds to theformula

    (113) H.sub.25 C.sub.12 --O--CH.sub.2 --NH--CO--NH--CH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.6 --H

if, in this example, instead of 100 mg of Ta(On--C₃ H₇)₅ the same amountof one of the following catalysts is employed, the same end product isobtained, with the corresponding yields shown below.

    ______________________________________                                        Example    Catalyst         Yield in %                                        ______________________________________                                        14                                                                                        ##STR16##       97                                                15         Ta(OnC.sub.5 H.sub.11).sub.5                                                                   95.2                                              16         Ta(OC(CH.sub.3).sub.3)Cl.sub.4                                                                 97.6                                              17         Ta(Ocyclododecane).sub.5                                                                       98.1                                              18         Nb(OnC.sub.9 H.sub.19).sub.5                                                                   95.2                                              19                                                                                        ##STR17##       96.5                                              20                                                                                        ##STR18##       92.8                                              21         Nb(O-cyclododecane).sub.5                                                                      95.2                                              22         Nb(OCH[CH.sub.3 ].sub.2).sub.4 Cl                                                              97.6                                              23         Nb(OCH[CH.sub.3 ].sub.2)Cl.sub.4                                                               97.0                                              24         Nb(OCH[CH.sub.3 ].sub.2).sub.5                                                                 95.8                                              25         W(OC[CH.sub.3 ].sub.3).sub.6                                                                   81.0                                              26         Zr(OnC.sub.4 H.sub.9).sub.4                                                                    99.0                                              27         Zr(OC[CH.sub.3 ].sub.3).sub.4                                                                  95.2                                              28         Zr(OCH.sub.3)Cl.sub.3                                                                          96.4                                              29         Zr(OC.sub.2 H.sub.4 Cl).sub.4                                                                  97.6                                              30         Ti(OnC.sub.3 H.sub.7).sub.4                                                                    97.0                                              ______________________________________                                    

We claim:
 1. A process for the manufacture of alkoxylated N-methylolcompound, which comprises reacting, at a temperature of 10° to 160° C.and a pressure of 1 to 20 atmospheres gauge, (a) a N-methylolated ureawith at most 22 carbon atoms with (b) an alkylene oxide of the formula##STR19## wherein R denotes hydrogen, alkyl with 1 to 3 carbon atoms,phenyl or a ##STR20## radical, in the presence of a catalytic amount of(c) at least one metal alcoholate of the formula

    Me(O--X).sub.r (Q).sub.n-r

wherein Me denotes a n-valent transition metal of groups IVB, VB, andVIB of the periodic system, X denotes alkyl with 1 to 4 carbon atoms,halogenoalkyl with 2 to 4 carbon atoms, phenyl, benzyl or cycloalkylwith at most 12 ring carbon atoms, Q denotes halogen or alkoxy with 1 to4 carbon atoms, r denotes 1 to n and n denotes 4, 5 or 6, or in thepresence of said component (c) together with (d) at least one alkalimetal hydroxide or one alkali metal alcoholate of an alkanol with 1 to 4carbon atoms.
 2. A process as defined in claim 1, wherein, a compound ofthe formula ##STR21## wherein Y denotes hydrogen, alkyl with 1 to 4carbon atoms or methylol and Z denotes alkyl with 1 to 22 carbon atoms,alkenyl with 3 to 22 carbon atoms, a monoalkylene glycol or polyalkyleneglycol radical with 2 or 3 carbon atoms per alkylene unit and with up to100 alkoxy groups in the chain, cycloalkyl with 5 to 14 ring carbonatoms, phenyl or benzyl, is used as the component (a).
 3. A process asdefined in claim 1, wherein ethylene oxide, propylene oxide,diglycidyl-ether or styrene oxide is used as the component (b).
 4. Aprocess as defined in claim 3, wherein ethylene oxide is used as thecomponent (b).
 5. A process as defined in claim 1, wherein at least onemetal alcoholate of the formula

    Me(OX').sub.n

wherein Me and n have the meaning indicated in claim 1 and X' denotesalkyl with 1 to 4 carbon atoms, phenyl, benzyl or cycloalkyl with atmost 12 ring carbon atoms, is used as the component (c).
 6. A process asdefined in claim 1, wherein at least one metal alcoholate of the formula

    Me.sub.1 (O--X).sub.n

wherein Me₁ denotes niobium^(V), tantalum^(V), tungsten^(VI),molybdenum^(VI), zirconium^(IV) or hafnium^(IV) and n denotes 4, 5 or 6,corresponding to the valency of the metal, and X has the meaningindicated in claim 1, is used as the component (c).
 7. A process asdefined in claim 6, wherein at least one metal alcoholate of the formula

    Me.sub.2 (O--X).sub.n.sbsb.1 '

wherein Me₂ denotes zirconium^(IV), niobium^(V), tantalum^(V) ortungsten^(VI) and n₁ denotes 4, 5 or 6, and X represents alkyl with 1 to4 carbon atoms, is used.
 8. A process as defined in claim 1, whereinsodium hydroxide or potassium hydroxide or a sodium alcoholate or apotassium alcoholate of an alkanol with 1 to 4 carbon atoms, is used ascomponent (d).
 9. A process as defined in claim 1, wherein the reactionis carried out at 30° to 120° C.
 10. A process as defined in claim 9,wherein the reaction is carried out at 40° to 90° C.
 11. A process asdefined in claim 1, wherein the reaction is carried out at a pressure of1 to 11 atmospheres gauge.
 12. A process as defined in claim 1, wherein0.05 to 5%, preferably 0.1 to 2%, relative to the weight of the reactionmixture, of the components (c) and (d) together are employed.
 13. Aprocess as defined in claim 12, wherein the components (c) and (d) areemployed in a weight ratio to one another of 9:1 to 1:9, preferably 4:1to 1:4.